Stabilizing a photosensitive composition containing an n-vinyl heterocyclic compound and an organic halogen compound with an azabicycloene compound

ABSTRACT

Images on photosensitive compositions made of N-vinyl heterocyclic and organic halogen compounds are stabilized in a solution of an azabicycloene compound such as 1,5-diazabicyclo (4,3,0) nonene-5 or 1,5-diazabicyclo (5,4,0) undecane-5-one. The stabilizing effect by azabicycloene can be enhanced by adding a heavy metal salt of a surface active agent to the solution.

United States Patent I1 1 [111 3,881,929

Asakawa 1 May 6, 1975 STABILIZING A PHOTOSENSITIVE [56] References CitedCOMPOSITION CONTAINING AN N-VINYL UNITED STATES PATENTS HETEROCYLICCOMPOUND AND AN 3,512,976 5/1970 Yamada et 96/90 R ORGANIC HALOGENCOMPOUND WITH AN AZABICYCLOENE COMPOUND FOREIGN PATENTS OR APPLICATIONS1,542,058 10/1968 France 96/90 R [75] Inventor. Shlrow Asakawa,Kawasaki, Japan 45-40553 12/1970 Japan l u 96/90 R [73] Assignee:Matsushita Electric Industrial Co,, 45-40554 12/1970 Japan 96/90 R LttL,Kadoma, Japan y Primary ExaminerWon Louie, Jr.

[21] Appl. No.: 364,315 [57] ABSTRACT Images on photosensitivecompositions made of N- [30] Foreign Apphcauon Priority Data vinylheterocyclic and organic halogen compounds are May Japan stabilized in asolution of an azabicycloene compound such as 1,5-diazabicyclo [4,3,0]nonenc-S or 1,5- [52] CL 96/48 R5 96/90 R; 260/2945 HN; diazabicyclo[5,4,0] undecane-S-one. The stabilizing 260/295 MN; 106/135 effect byazabicycloene can be enhanced by adding a Int. heavy metal alt of aurface active agent to the sol [58] Field of Search 96/48 R, 90 R;260/239, do

260/296 HN, 29.6 MN; 106/135 7 Claims, No Drawings STABILIZING APHOTOSENSITIVE COMPOSITION CONTAINING AN N-VINYL I-IETEROCYCLIC COMPOUNDAND AN ORGANIC HALOGEN COMPOUND WITH AN AZABICYCLOENE COMPOUND Thisinvention relates generally to a photographic composition. Moreparticularly, it relates to a photographic image stabilizer used forstabilizing images obtained with organic photosensitive compositionscomprising N-vinyl heterocyclic and organic halogen compounds.

Photographic images produced in an organic photosensitive coating onbaryta paper are liable to color change when subjected to daylightexposure for a period of 3 to 7 days. During this period, ayellow-tobrown color change would take place in the lightstruck areas,and a further exposure to daylight would turn the whole areas to brown.Such color change is detrimental to the preservation of photographicimages for an extended period of time.

Color change may be attributable to a number of factors which includephoto-oxidization of dyes p'roduced upon exposure to light, subsequentphotoreaction of the unexposed areas, and a subsequent photo-reaction ofunreacted substances which may be present in the dyes. Color change mayalso depend on the amount of organic halogen compounds present in thelightexposed areas.

For purposes of stabilizing images, additives and stabilizers have beenproposed which include peroxides (U.S. Pat. No. 3,544,320),aldehyde-NaHSO (U.S. Pat. No. 3,503,742), Na SO and NaHSO (U.S. Pat. No.3,512,976) and various mixtures thereof (U.S. Pat. No. 3,544,322). Thesestabilizers, however, are still unsatisfactory in terms of its qualitydue to inherent color change.

it is accordingly an object of the present invention to provide animproved image stabilizer which, when applied to light-exposed areas ofa photosensitive film, decomposes unreacted alkylhalides which may bepresent in the film to render them insensitive to further exposure tolight.

In accordance with a first preferred embodiment of the invention, theimage stabilizer comprises as its main constituent an azabicycloenecompound ofa cyclic amidine expressed generally by the followingformula:

icu i where m and n are integers from 2 to 6. The image stabilizeraccording to the invention is obtained by dissolving 0.5 to 20% byweight of the azabicycloene compound into an aqueous solution of, forexample, about 20% polyvinyl alcohol. A preferred value of theazabicycloene content in the solution is from 4 to l% by weight.Examples of the azabicycloene compounds employed in the practice of thepresent invention are l,5-diazabicyclo [5,4,0] undecane-S ene and 1,5-diazabicyclo [4,3,0] nonene-S. These azabicycloene compounds may bedissolved either in water, in an aqueous solution containing awater-soluble resin or a polymer dissolving organic solvent organic. Thelightexposed film may be dipped into the solution or it may be sprayedor wiped with the solution and the solvent is then removed by drying thefilm in the ambient atmosphere. These azabicycloene compounds arestrongly alkaline and therefore they serve to decompose organic halogencompounds present in the light-exposed areas as intermediates of aphoto-reaction to thereby stabilize the images formed. The desensitizingcompounds would allow the whiteness of background areas to increase,which would otherwise turn to light yellowgreen. This could result in anincrease in the image contrast. These azabicycloene compounds also havea desensitizing effect on this background areas by increasing theirwhiteness while penetrating deeply into the photosensitive compositionwith the aid of a heavy metal salt of a surface active agent which willbe described hereinbelow. The desensitizing effect is enhanced byheating the film at a temperature of about 50C for a period of about 30seconds.

The aforementioned water soluble resin may be natural high polymers suchas gelation and agar-agar, or polyvinyl alcohol, polyethylene glycol,polyacrylamide, polyvinylpyrrolidone and polyacryl acid. The organicsolvent may be, for example, alcohol, acetone, tetrahydrofuran,dimethylformamide, etc. As polymers dissolved in one of the above-statedorganic solvents, such substances as polyacrylate, polyvinyl compounds,polycondensated compounds including polyamid derivatives may be used.

ln a second preferred embodiment, the present invention contemplates theuse of other compounds as additives to the azabicycloene compounds suchas a heavy metal salt of a surface active agent such as sulfate,sulfonate, or phosphate. The surface active agent (usually a sodiumsalt) enhances the desensitizing effect when added to the imagestabilizer of a photosensitive composition containing a water-solubleresin such as gelatin, because the surface active agent serves to swellthe gelatin, thus allowing the azabicycloene com pound to penetrate deepinto the composition. The desensitizing effect can be further enhancedby the use of a heavy metal salt such as, for example, a zinc, tin or aniron salt. In the practice of the invention, the additive to theazabicycloene compounds may preferably be heavy metal laurylsulfate,oleylsulfate, stearylsulfate, laurylsulfonate,dibutylnaphtalenesulfonate, dodecylbenzenesulfonate, oleyletherphosphateand laurylphosphate. More preferably, the additive may beZn-dibutyl-naphthalenesulfonate or stannous sulfonate. These additivesare used in a concentration of about 0.5 to 20 weight percent in thesolvent. Synthesis of the azabicycloene compounds suitable for theinvention is known as briefly described hereinafter, and theabove-mentioned preferred two azabicycloene compounds are disclosed byAldrich Co. W. Reppe et al in Annalen de Chemie," Vol. 596, p. 210(1950)and by H. Oediger et al in Chemische Berichte," Vol. 99, p. 2012 (1966)where the synthesis of azabicycloene compounds is reported. For example,1,5-diazabicyclo(4,3,0)nonene-5 is prepared from pyrrolidone. In thefirst place, pyrrolidone is reacted with acrylonitrile by heating in thepresence of potassium hydroxide and hydroquinone. The product isacidified with hydrochloric acid and then concentrated under a reducedpressure to give I-( 2-cyanoethyl )-pyrrolidone. The thus obtainednitrile is dissolved in a mixture of methanol and ammonia and subjectedto catalytic reduction by the use of a Ni-Al catalyst, followed byfiltration, vacuum concentration and vacuum distillation. The distilledproduct, which is l-( 3-aminopropyl)-pyrrolidone, is then dissolved inxylol and admixed with p-toluenesulfonic acid, followed by reflux for adehydration reaction. The final reaction product is subjected tofiltration and vacuum distillation.

All the above sulfates, sulfonates and phosphates are well known and arecommercially available surface active agents as their respective sodiumsalts. The heavy metal salts for the stabilizer of the invention areknown and can be easily obtained by usual replacement reactions of suchsodium salts with, e.g., chlorides of the preferred heavy metals, whichreactions require no detailed description for one skilled in generalchemistry.

The invention will be described in detail by way of examples.

EXAMPLE l First, a photosensitive composition was prepared by mixing andthoroughly stirring the following constituents at high speed:

N-vinylcarbazol g. 4-p-dimethylaminostylquinolinc 6mg. Carbontetrabromide 4g. Water 80mg.

A sheet of baryta paper was coated with the thus obtained composition.

The photosensitive film thus formed on the baryta paper had a wetthickness of microns. After the coated sheet had been dried, it wassubjected to an imagewise exposure by a 250 watt xenon lamp from adistance of about I meter for 1 second through a suitable image patternplaced in an intermediate position between the lamp and the film. Asecond exposure was made by subjecting the film to light of wavelengthsabove 5300 A from a 100 watt tungsten lamp through an optical filter fora period of 5 seconds. A negative image was produced in the film when itwas left under the influence of ambient light radiation.

Second, a stabilizer was prepared by mixing the following constituentsand the image produced on the baryta paper was coated with the mixture:

l ,5 diazabicyclo (5,4,0] undecane5-cne 4g. Polyvinylalcohol 20g. WaterlDOml.

The stabilizer coated film was heated to, and kept at 50C for 30seconds: For purposes of comparison, a separate negative image withoutthe stabilizer coating was also produced in the same manner as describedabove and exposed to the radiation of a 40 watt fluorescent light from adistance of 30cm. The light-exposed areas started to change their colorto yellow in 3 days and turned totally brown within one week. Incontrast, the stabilizer-coated image did not appreciably change incolor even after a one-week exposure to the same fluorescent radiation.

EXAMPLE 2 First, a photosensitive composition was prepared by mixing andthoroughly stirring the following constituents:

N vinylcarbaml 10g. Tctrabromoethanc 4g.4-p-dimcthylaminostyrylquinolinc 6mg, Gelatin 20g. Water Bml.

A sheet of baryta paper was coated with the thus obtained composition.The photosensitive film was subjected to light exposures as described inExample I to develop a negative image.

Second, a stabilizer was prepared by mixing the following constituentsand the image produced on the baryta paper was coated with the mixture:

Lidiazabicyclo 4,3,0 nonene-S 8g. Polyvinylalcohol 20g. Water l00ml.

A similar desensitizing effect was observed as in Example 1 when thefilm was subjected to a one-week exposure to the 40 watt fluorescentlight.

EXAMPLE 3 The same procedures as in Example I were repeated except thatthe components of the stabilizer were re placed by the followingconstituents:

1,5-diazabicyclo 4,3,0 nonene 2g. Zndibutylnaphtalenesulfonate 2g.Polyvinylalcohol 20g. Water 40ml:

No appreciable color change was observed after a one-week exposure tothe 40 watt fluorescent radiation.

EXAMPLE 4 The same procedures as in Example 2 were repeated except thatthe components of the stabilizer were replaced by the followingconstituents:

LS-diazabicyclo I 5,4,0 undecane5-ene 3g. Stannous sulfosuccinatc 3g.Polyvinylalcohol 5g. Water 50ml:

where m and n are each an integer ranging from 2 to 6; and drying thewet image and background areas at a temperature ranging from roomtemperature to 50C.

2. A process as claimed in claim 1, wherein said aqueous solutionfurther contains up to 50% by weight of a water-soluble resin selectedfrom the group consisting of gelatin, agar-agar, polyvinyl alcohol,polyethylene glycol, polyacrylamide, polyvinylpyrrolidone and polyacrylacid.

3. A process as claimed in claim 2, wherein said aqueous solutionfurther contains 0.5 to by weight of a heavy metal salt of a surfaceactive agent selected from the group consisting of a sulfate, sulfonateand phosphate, said heavy metal being selected from the group consistingof zinc, tin and iron.

4. A process as claimed in claim 1, wherein said azabicycloene compoundis selected from the group consisting of l,5-diazabicyclo(4,3,0)nonene-5 and 1,5-

tration of which in said solvent is about 6% by weight. 4

1. A PROCESS OF STABILIZING IMAGE AND BACKGROUND AREAS PRODUCED BYEXPOSURE TO LIGHT OF A PHOTOSENSITIVE COMPOSITION CONTAINING AN N-VINYLHETEROCYCLIC COMPOUND AND AN ORGANIC HALOGEN COMPOUND, THE PROCESSCOMPRISING THE STEPS OF: WETTING THE IMAGE AND BACKGROUND AREAS WITH ANAQUEOUS SOLUTION OF 0.5 TO 20% WEIGHT OF AN AZABICYCLOENE COMPOUND OF ACYCLIC AMIDINE REPRESENTED BY THE FORMULA -N<(-(CH2)N-C(-)=N-(CH2)M-),WHERE THE FIRST N AND THE C HAVING THE FREE BOND ARE JOINED WHERE M ANDN ARE EACH AN INTEGER RANGING FROM 2 TO 6; AND DRYING THE WET IMAGE ANDBACKGROUND AREAS AT A TEMPERATURE RANGING FROM ROOM TEMPERATURE TO 50*C.2. A process as claimed in claim 1, wherein said aqueous solutionfurther contains up to 50% by weight of a water-soluble resin selectedfrom the group consisting of gelatin, agar-agar, polyvinyl alcohol,polyethylene glycol, polyacrylamide, polyvinylpyrrolidone and polyacrylacid.
 3. A process as claimed in claim 2, wherein said aqueous solutionfurther contains 0.5 to 20% by weight of a heavy metal salt of a surfaceactive agent selected from the group consisting of a sulfate, sulfonateand phosphate, said heavy metal being selected from the group consistingof zinc, tin and iron.
 4. A process as claimed in claim 1, wherein saidazabicycloene compound is selected from the group consisting of1,5-diazabicyclo(4,3,0)nonene-5 and1,5-diazabicyclo(5,4,0)undecane-5-ene.
 5. A process as claimed in claim3 wherein said sulfate is selected from the group consisting oflaurylsulfates, oleylsulfates and stearylsulfates, said sulfonate isselected from the group consisting of laurylsulfonate,dibutylnaphthalenesulfonates and dodecylbenzenesulfonates, and saidphosphate is selected from the group consisting of oleyletherphosphatesand laurylphosphates.
 6. A process as claimed in claim 3 wherein saidheavy metal sulfonate is Zn-dibutylnaphthalenesulfonate, theconcentration of which in said solvent is about 5% by weight.
 7. Aprocess as claimed in claim 3 wherein said heavy metal sulfonate isstannous sulfosuccinate, the concentration of which in said solvent isabout 6% by weight.